Epoxy resin composition

Abstract

To provide a polymer composition excellent in adhesiveness to a wide range of materials and impact absorption.SOLUTION: The present invention provides an epoxy resin composition which contains: a hydrogenated block copolymer composition containing a hydrogenated block copolymer (A) represented by the following general formula (A) and a hydrogenated block copolymer (B) represented by the following general formula (B); an epoxy resin (C); and a curing agent (D). Ar1A-HDA-Ar2A (A). Ar1B-HDB-Ar2B (B). (In the general formulae (A) and (B), Ar1A, Ar2A, Ar1B and Ar2B are each an aromatic vinyl polymer block, HDA and HDB are each a hydrogenated polymer block of a conjugated diene polymer, the ratio of weight average molecular weights Mw(Ar2A) / Mw(Ar1A) is 3.0-20, and the ratio of weight average molecular weights Mw(Ar2B) / Mw(Ar1B) is 0.95-1.05.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an epoxy resin composition, and more particularly to an epoxy resin composition that has excellent adhesion to a wide range of materials and excellent impact absorption properties. [Background technology]

[0002] Epoxy resins are used as adhesives. Epoxy adhesives include one-component epoxy adhesives containing an epoxy resin and a latent curing agent, and two-component epoxy adhesives containing an epoxy resin and a curing agent, and are used for a variety of purposes (see, for example, Patent Document 1). However, the impact absorption of epoxy adhesives is insufficient, and improvements in impact absorption are desired. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-6525 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide an epoxy resin composition that has excellent adhesion to a wide range of materials and excellent impact absorption properties. [Means for solving the problem]

[0005] The present inventors have conducted studies to achieve the above-mentioned object, and have found that the above-mentioned object can be achieved by blending a hydrogenated block copolymer composition containing two types of hydrogenated block copolymers having specific structures with a composition containing an epoxy resin (C) and a curing agent (D), thereby completing the present invention.

[0006] That is, according to the present invention, the following epoxy resin composition is provided.

[0007] [1] An epoxy resin composition comprising a hydrogenated block copolymer composition including a hydrogenated block copolymer (A) represented by the following general formula (A) and a hydrogenated block copolymer (B) represented by the following general formula (B), an epoxy resin (C), and a curing agent (D): Ar1 A -HD A -Ar2 A (A) Ar1 B -HD B -Ar2 B (B) (In the general formula (A) and the general formula (B), Ar1 A , Ar2 A , Ar1 B , and Ar2 B is an aromatic vinyl polymer block, and HD A and HD B is a hydrogenated polymer block of a conjugated diene polymer, and Ar1 A Weight average molecular weight (Mw(Ar1 A )) for Ar2 A Weight average molecular weight (Mw(Ar2 A )) ratio (Mw(Ar2 A ) / Mw(Ar1 A )) is 3.0 to 20, and Ar1 B Weight average molecular weight (Mw(Ar1 B )) for Ar2 B Weight average molecular weight (Mw(Ar2 B )) ratio (Mw(Ar2 B ) / Mw(Ar1 B )) is 0.95 to 1.05. [2] The epoxy resin composition according to [1], wherein the weight ratio (A / B) of the hydrogenated block copolymer (A) to the hydrogenated block copolymer (B) in the hydrogenated block copolymer composition is 10 / 90 to 80 / 20. [3] The epoxy resin composition according to [1] or [2], wherein at least a portion of the hydrogenated block copolymer constituting the hydrogenated block copolymer composition has a silane-containing functional group. [4] The epoxy resin composition according to any one of [1] to [3], wherein the weight ratio ((C+D) / (A+B)) of the total content of the epoxy resin (C) and the curing agent (D) to the total content of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) is 99 / 1 to 70 / 30. [5] The epoxy resin composition according to any one of [1] to [4], wherein the proportion of aromatic vinyl monomer units in the hydrogenated block copolymer composition is 20 to 60% by weight based on the total weight of all polymer components. [6] The epoxy resin composition according to any one of [1] to [5], wherein the hydrogenation rate of the olefin in the hydrogenated block copolymer composition is 10 to 100%. [7] Ar1 in general formula (A) and general formula (B) A , Ar1 B , and Ar2 B The weight average molecular weight of each of the Ar2 in the general formula (A) is 1,000 to 40,000. A The weight average molecular weight of the HD copolymer in the general formula (A) is 5,000 to 250,000. a and HD in general formula (B) b The epoxy resin composition according to any one of [1] to [6], wherein each of the weight average molecular weights of the above is 10,000 to 300,000. [8] The epoxy resin composition according to any one of [1] to [7], wherein the hydrogenated block copolymer composition has a weight average molecular weight of 20,000 to 500,000. [9] The epoxy resin composition according to any one of [1] to [8], which is an adhesive for electronic substrates, a structural adhesive for automobiles, a structural adhesive for aircraft, a structural adhesive for sports components, or an interlayer film for bulletproof vests. [Effects of the Invention]

[0008] According to the present invention, an epoxy resin composition having excellent adhesive properties to a wide range of materials and excellent impact absorption properties can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0009] The epoxy resin composition of the present invention contains a hydrogenated block copolymer composition containing the hydrogenated block copolymer (A) described below and the hydrogenated block copolymer (B) described below, an epoxy resin (C), and a curing agent (D).

[0010] <Hydrogenated Block Copolymer Composition> The hydrogenated block copolymer composition used in the present invention contains the hydrogenated block copolymer (A) described below and the hydrogenated block copolymer (B) described below. According to the present invention, by blending a hydrogenated block copolymer composition containing two types of hydrogenated block copolymers having unique structures with a composition containing an epoxy resin (C) and a curing agent (D), it is possible to obtain excellent adhesion to a wide range of materials and excellent impact absorption properties.

[0011] Ar1 A -HD A -Ar2 A (A) Ar1 B -HD B -Ar2 B (B)

[0012] In the general formula (A) and the general formula (B), Ar1 A , Ar2 A , Ar1 B , and Ar2 B is an aromatic vinyl polymer block, and HD A and HD B is a hydrogenated polymer block of a conjugated diene polymer, and Ar1 A Weight average molecular weight (Mw(Ar1 A )) for Ar2 A Weight average molecular weight (Mw(Ar2 A )) ratio (Mw(Ar2 A ) / Mw(Ar1 A )) is 3.0 to 20, and Ar1 B Weight average molecular weight (Mw(Ar1 B )) for Ar2 B Weight average molecular weight (Mw(Ar2 B )) ratio (Mw(Ar2 B ) / Mw(Ar1 B)) is 0.95 to 1.05.

[0013] Aromatic vinyl polymer block Ar1 constituting the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) A , Ar2 A , Ar1 B , and Ar2 B is a polymer block composed of aromatic vinyl monomer units.

[0014] The aromatic vinyl monomer used to form the aromatic vinyl monomer unit is not particularly limited as long as it is an aromatic vinyl compound. Examples of aromatic vinyl compounds include styrene; alkyl-substituted styrenes such as α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, and 5-t-butyl-2-methylstyrene; halogen-substituted styrenes such as 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 4-bromostyrene, 2-methyl-4,6-dichlorostyrene, and 2,4-dibromostyrene; and vinylnaphthalene. Among these, styrene is preferred. These aromatic vinyl monomers can be used alone or in combination of two or more in each aromatic vinyl polymer block. Furthermore, the same or different aromatic vinyl monomers can be used in each aromatic vinyl polymer block.

[0015] The content of aromatic vinyl monomer units in each aromatic vinyl polymer block is preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably substantially 100% by weight, based on the total weight of the aromatic vinyl polymer block.

[0016] Also, the aromatic vinyl polymer block Ar1 A , Ar2 A , Ar1 B, and Ar2 B may each contain a monomer unit other than the aromatic vinyl monomer unit. Examples of the monomer constituting the monomer unit other than the aromatic vinyl monomer unit include conjugated diene monomers such as 1,3-butadiene and isoprene (2-methyl-1,3-butadiene); α,β-unsaturated nitrile monomers; unsaturated carboxylic acid or acid anhydride monomers; unsaturated carboxylic acid ester monomers; and non-conjugated diene monomers.

[0017] The content of monomer units other than aromatic vinyl monomer units in each aromatic vinyl polymer block is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably substantially 0% by weight, based on the total weight of the aromatic vinyl polymer block.

[0018] Hydrogenated block copolymer (A) and hydrogenated block copolymer (B) are composed of hydrogenated block copolymer (HD) and hydrogenated block copolymer (HD) of conjugated diene polymer. A and HD B is a polymer block constituted by conjugated diene monomer units, and at least a portion of the conjugated diene monomer units constituting the polymer block are hydrogenated.

[0019] The conjugated diene monomer used to form the conjugated diene monomer unit is not particularly limited as long as it is a conjugated diene compound. Examples of conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Among these, 1,3-butadiene and / or isoprene are preferred from the viewpoint of polymerization reactivity, and isoprene is particularly preferred. These conjugated diene monomers can be used alone or in combination of two or more in each hydrogenated polymer block. Furthermore, the same conjugated diene monomer or different conjugated diene monomers can be used in each hydrogenated polymer block.

[0020] The content of conjugated diene monomer units (including hydrogenated conjugated diene monomer units) in each hydrogenated polymer block is preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably substantially 100% by weight, based on the total weight of the conjugated diene polymer block.

[0021] Hydrogenated block HD polymer of conjugated diene polymer A and HD B may each contain a monomer unit other than the conjugated diene monomer unit. Examples of the monomer constituting the monomer unit other than the conjugated diene monomer unit include aromatic vinyl monomers such as styrene and α-methylstyrene; α,β-unsaturated nitrile monomers; unsaturated carboxylic acid or acid anhydride monomers; unsaturated carboxylic acid ester monomers; and non-conjugated diene monomers.

[0022] The content of monomer units other than conjugated diene monomer units (including hydrogenated conjugated diene monomer units) in each hydrogenated polymer block is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably substantially 0% by weight, based on the total weight of the conjugated diene polymer block.

[0023] Hydrogenated block HD polymer of conjugated diene polymer A and HD B The vinyl bond content before hydrogenation (the proportion of 1,2-vinyl bonds and 3,4-vinyl bonds in all conjugated diene monomer units) is preferably 1 to 80 mol %, more preferably 3 to 20 mol %, and even more preferably 5 to 12 mol %. By keeping the vinyl bond content within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved. Hydrogenated polymer block HD of conjugated diene polymer A and HD B The vinyl bond content before hydrogenation was measured using deuterated chloroform as a solvent. 1 It can be determined by H-NMR.

[0024] The hydrogenated block copolymer (A) is Ar1 AWeight average molecular weight (Mw(Ar1 A )) for Ar2 A Weight average molecular weight (Mw(Ar2 A )) ratio (Mw(Ar2 A ) / Mw(Ar1 A )) is in the range of 3.0 to 20. That is, the hydrogenated block copolymer (A) is a block copolymer containing an aromatic vinyl polymer block Ar1 having a relatively small weight average molecular weight. A , hydrogenated polymer block HD of conjugated diene polymer A and an aromatic vinyl polymer block Ar2 having a relatively high weight average molecular weight A It is a hydrogenated product of an asymmetric aromatic vinyl-conjugated diene-aromatic vinyl block copolymer composed of these units in this order.

[0025] In the hydrogenated block copolymer (A), Mw(Ar2 A ) / Mw(Ar1 A ) is 3.0 to 20. Mw(Ar2 A ) / Mw(Ar1 A If Mw(Ar2) is too small or too large, it becomes difficult for the hydrogenated block copolymer to have both excellent adhesion to a wide range of materials and excellent impact absorption. A ) / Mw(Ar1 A ) is preferably in the range of 4.0 to 16, more preferably in the range of 5.0 to 13. A ) / Mw(Ar1 A ) in the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0026] In the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer or polymer block are determined as polystyrene-equivalent values ​​measured by high performance liquid chromatography.

[0027] Aromatic vinyl polymer block Ar1 with relatively low weight-average molecular weight A Weight average molecular weight (Mw(Ar1 A)) is preferably 1,000 to 40,000, more preferably 2,000 to 15,000, and even more preferably 3,000 to 8,000.

[0028] Aromatic vinyl polymer block Ar2 with relatively high weight average molecular weight A Weight average molecular weight (Mw(Ar2 A )) is preferably 5,000 to 250,000, more preferably 10,000 to 120,000, and even more preferably 20,000 to 80,000.

[0029] Hydrogenated block HD polymer of conjugated diene polymer A Weight average molecular weight (Mw(HD A )) is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, even more preferably 15,000 to 150,000, and particularly preferably 20,000 to 80,000.

[0030] The weight average molecular weight of the hydrogenated block copolymer (A) as a whole is not particularly limited, but is preferably 20,000 to 500,000, more preferably 25,000 to 300,000, and even more preferably 30,000 to 150,000.

[0031] By setting the weight average molecular weight of the hydrogenated block copolymer (A) and the weight average molecular weight of each polymer block within the above ranges, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0032] The content of aromatic vinyl monomer units relative to the total monomer units of the hydrogenated block copolymer (A) is not particularly limited, but is preferably 20 to 90% by weight, more preferably 30 to 90% by weight, even more preferably 40 to 85% by weight, and particularly preferably 45 to 85% by weight. By setting the content of aromatic vinyl monomer units within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved. The content of aromatic vinyl monomer units can be determined based on the detection intensity ratio between a differential refractometer and an ultraviolet detector in high-performance liquid chromatography measurement.

[0033] The hydrogenated block copolymer (B) is a symmetric triblock copolymer represented by the general formula (B). The hydrogenated block copolymer (B) is a conjugated diene polymer block HD. B At each end of the B , Ar2 B It is a hydrogenated aromatic vinyl-conjugated diene-aromatic vinyl block copolymer composed of the following:

[0034] In the hydrogenated block copolymer (B), Mw(Ar2 B ) / Mw(Ar1 B ) is not particularly limited as long as it is 0.95 to 1.05, but is preferably 0.97 to 1.03. B ) / Mw(Ar1 B ) in the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0035] Aromatic vinyl polymer block Ar1 B and Ar2 B Weight average molecular weight (Mw(Ar1 B ) and Mw(Ar2 B Mw(Ar1) is preferably 1,000 to 40,000, more preferably 2,000 to 15,000, and even more preferably 3,000 to 8,000. B ) and Mw(Ar2 B) in the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0036] In addition, these two aromatic vinyl polymer blocks Ar1 B and Ar2 B At least one polymer block of the B ), Mw(Ar2 B )) is an aromatic vinyl polymer block Ar1 having a relatively small weight average molecular weight, which constitutes the hydrogenated block copolymer (A). A Weight average molecular weight (Mw(Ar1 A )) may be equal to or different from, but it is more preferable that they are substantially equal to. For example, Ar1 A Weight average molecular weight (Mw(Ar1 A )) for Ar1 B Weight average molecular weight (Mw(Ar1 B )) ratio (Mw(Ar1 B ) / Mw(Ar1 A )) may be in the range of 0.9 to 2.2, and the ratio is preferably in the range of 0.95 to 1.05.

[0037] Hydrogenated block HD polymer of conjugated diene polymer B Weight average molecular weight (Mw(HD B )) is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, even more preferably 15,000 to 150,000, and particularly preferably 20,000 to 80,000.

[0038] Hydrogenated block HD polymer of conjugated diene polymer B Weight average molecular weight (Mw(HD B ) is a hydrogenated polymer block HD of a conjugated diene polymer that constitutes the hydrogenated block copolymer (A). A Weight average molecular weight (Mw(HD A )) may be equal to or different from, but it is more preferable that they are substantially equal. For example, HD A Weight average molecular weight (Mw(HDA )) against HD B Weight average molecular weight (Mw(HD B )) ratio (Mw(HD B ) / Mw(HD A )) is preferably in the range of 0.95 to 1.05.

[0039] The weight average molecular weight of the hydrogenated block copolymer (B) as a whole is not particularly limited, but is preferably 20,000 to 500,000, more preferably 25,000 to 300,000, and even more preferably 30,000 to 150,000.

[0040] By setting the weight average molecular weight of the hydrogenated block copolymer (B) and the weight average molecular weight of each polymer block within the above ranges, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0041] The content of aromatic vinyl monomer units relative to the total monomer units of the hydrogenated block copolymer (B) is not particularly limited, but is preferably 7 to 60% by weight, more preferably 10 to 50% by weight, and even more preferably 15 to 40% by weight. By setting the content of aromatic vinyl monomer units within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0042] When a production method using a coupling agent is adopted in producing the hydrogenated block copolymer composition used in the present invention, the hydrogenated polymer block of the conjugated diene polymer (for example, HD B ) may contain a residue of a coupling agent. Specifically, the hydrogenated block copolymer (B) may be a compound represented by the following formula: Ar1 B -(HD B’ -X-HD B’’ )-Ar2 B

[0043] That is, as shown in the above formula, the hydrogenated polymer block HD of the conjugated diene polymer BHowever, HD is reacted with the coupling agent residue X. B’ , HD B’’ The residue X of the coupling agent may be a residue of a bifunctional coupling agent, which will be described later.

[0044] The hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) constituting the hydrogenated block copolymer composition used in the present invention, and each of the polymer blocks constituting these, have a molecular weight distribution, represented by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) [(Mw) / (Mn)], which is not particularly limited, but is preferably 1.1 or less, more preferably 1.05 or less.

[0045] The hydrogenated block copolymer composition used in the present invention may, for example, contain only the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) as polymer components.

[0046] The weight ratio (A / B) of the hydrogenated block copolymer (A) to the hydrogenated block copolymer (B) in the hydrogenated block copolymer composition used in the present invention is not particularly limited, but is preferably 10 / 90 to 80 / 20, more preferably 20 / 80 to 60 / 40, and even more preferably 25 / 75 to 50 / 50. By setting the weight ratio (A / B) within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved. The weight ratio (A / B) can be determined from the area ratio of the peaks corresponding to each block copolymer in a chart obtained by high-performance liquid chromatography.

[0047] The hydrogenation rate of the olefin in the hydrogenated block copolymer composition used in the present invention is preferably 10 to 100%, more preferably 50 to 100%, even more preferably 80 to 100%, particularly preferably 90 to 100%, and most preferably 95 to 100%. By setting the hydrogenation rate of the olefin within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0048] Here, the hydrogenation rate of olefins refers to the hydrogenation rate of olefins in all polymer components constituting the hydrogenated block copolymer composition, and specifically refers to the proportion (mol %) of hydrogenated non-aromatic carbon-carbon double bonds in the total non-aromatic carbon-carbon double bonds contained in the hydrogenated block copolymer composition before hydrogenation. 1 It can be determined by H-NMR spectroscopy.

[0049] The weight-average molecular weight of all the polymer components constituting the hydrogenated block copolymer composition used in the present invention is not particularly limited, but is preferably 20,000 to 500,000, more preferably 30,000 to 400,000, even more preferably 35,000 to 150,000, and particularly preferably 40,000 to 100,000. By setting the weight-average molecular weight within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0050] Furthermore, the molecular weight distribution, which is expressed as the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of all the polymer components constituting the hydrogenated block copolymer composition used in the present invention, is not particularly limited, but is preferably 1 to 2, more preferably 1.001 to 1.5, and even more preferably 1.01 to 1.15.

[0051] The proportion of aromatic vinyl monomer units in the entire polymer components (total monomer units constituting the polymer components) in the hydrogenated block copolymer composition used in the present invention (hereinafter sometimes referred to as "total aromatic vinyl monomer unit content") is not particularly limited, but is preferably 10 to 90% by weight, more preferably 15 to 75% by weight, and even more preferably 20 to 60% by weight. By setting the total aromatic vinyl monomer unit content within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved. The total aromatic vinyl monomer unit content can be determined by the following formula: 1 It can be determined by H-NMR measurement.

[0052] In addition, when all polymer components constituting the hydrogenated block copolymer composition are composed only of aromatic vinyl monomer units and conjugated diene monomer units, the polymer components in the hydrogenated block copolymer composition can be decomposed by ozonolysis and then reduced with lithium aluminum hydride according to the method described in Rubber Chem. Technol., 45, 1295 (1972). This decomposes the conjugated diene monomer unit portions (including hydrogenated portions), allowing only the aromatic vinyl monomer unit portions to be isolated, thereby easily measuring the total aromatic vinyl monomer unit content. The aromatic vinyl monomer unit content and conjugated diene monomer unit content in each block copolymer can be determined by a similar method.

[0053] At least a portion of the hydrogenated block copolymers constituting the hydrogenated block copolymer composition used in the present invention preferably has a silane-containing functional group. That is, the hydrogenated block copolymer composition preferably contains a hydrogenated block copolymer having a silane-containing functional group. In this case, the hydrogenated block copolymer may have one or more types of silane-containing functional groups. Furthermore, the hydrogenated block copolymer composition may contain hydrogenated block copolymers having different silane-containing functional groups.

[0054] When at least a part of the hydrogenated block copolymer constituting the hydrogenated block copolymer composition has a silane-containing functional group, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0055] The silane-containing functional group is preferably a modified group derived from an unsaturated silane modifier. Here, the unsaturated silane modifier is preferably a silane compound containing a carbon-carbon unsaturated bond in the molecule, more preferably a compound (1) represented by the following general formula (1): [ka] (In the above general formula (1), R 1 ~R 3are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R 4 is a hydrocarbon group having a carbon-carbon unsaturated bond.

[0056] In general formula (1), R 1 ~R 3 are not particularly limited as long as they are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. 1 ~R 3 The alkyl group and alkoxy group represented by R may be linear, branched, or may contain a cyclic structure. 2 ~R 4 may be the same or different.

[0057] R 1 ~R 3 As R, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms are preferred, and an alkoxy group having 1 to 6 carbon atoms is more preferred. 1 ~R 3 The number of carbon atoms in each of R may be independently 0 to 6, preferably 0 to 4, more preferably 0 to 2, and even more preferably 1 (methyl group or methoxy group). 1 ~R 3 By having the above structure, the effects of the present invention can be enhanced.

[0058] In general formula (1), R 1 ~R 3 At least one of R is preferably an alkoxy group having 1 to 6 carbon atoms. 1 ~R 3 It is more preferable that at least two of R are alkoxy groups having 1 to 6 carbon atoms. 1 ~R 3 It is more preferable that all of the groups are alkoxy groups having 1 to 6 carbon atoms.

[0059] In general formula (1), R 4 is not particularly limited as long as it is a hydrocarbon group having a carbon-carbon unsaturated bond.4 R may be linear, branched, or may contain a cyclic structure. 4 Examples of R include vinyl group-containing hydrocarbon groups such as vinyl group, allyl group, 1-methylethenyl group, and 3-butenyl group; and alkynyl groups such as propynyl group, with vinyl group-containing hydrocarbon groups being preferred. 4 The number of carbon atoms in R is not particularly limited, but is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 (vinyl group). 4 By having the above structure, the effects of the present invention can be enhanced.

[0060] For example, R 4 is a vinyl group-containing hydrocarbon group, the compound (1) is a compound (2) represented by the following general formula (2). [ka]

[0061] In the above general formula (2), R 1 ~R 3 are the groups described above, and R 5 is a single bond or a divalent hydrocarbon group. 5 The hydrocarbon group as -R in general formula (2) may be linear, branched, or may contain a cyclic structure. 5 -CH=CH2 is -R in general formula (1) 4 Corresponds to.

[0062] For example, by using compound (2) as an unsaturated silane modifier, it is possible to introduce into the hydrogenated block copolymer a group (3) (silane-containing functional group) represented by the following general formula (3) as a modifying group derived from compound (2). [ka]

[0063] The unsaturated silane modifier is preferably a compound (4) represented by the following general formula (4). [ka]

[0064] In general formula (4), R 6 ~R 8 are each independently an alkyl group having 1 to 6 carbon atoms, and R 9 is a single bond or an alkylene group having 1 to 4 carbon atoms. 6 , -OR 7 , and -OR 8 respectively represent -R in the general formulas (1) to (3). 1 , -R 2 , and -R 3 Corresponding to R in general formula (4), 9 represents R in general formulas (2) to (3). 5 Corresponds to.

[0065] R 6 ~R 8 Each of R may be linear, branched, or may contain a cyclic structure. 6 ~R 8 may be the same or different. 6 ~R 8 may each independently have 1 to 6 carbon atoms, preferably 1 to 4, more preferably 1 or 2 (methyl group, ethyl group), and even more preferably 1 (methyl group).

[0066] R 9 R may be linear, branched, or may contain a cyclic structure. 9 The number of carbon atoms in may be 0 to 4, preferably 0 to 2, more preferably 0 or 1, and even more preferably 0 (single bond).

[0067] The amount of silane-containing functional groups in the hydrogenated block copolymer composition used in the present invention is not particularly limited. The amount of silane-containing functional groups per 100 g of the hydrogenated block copolymer composition is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, and even more preferably 1 to 30 mmol. By setting the amount of silane-containing functional groups within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0068] The hydrogenated block copolymer composition used in the present invention is preferably a silane-modified hydrogenated block copolymer composition (I) having a silane-containing functional group, which is obtained by modifying the unmodified hydrogenated block copolymer composition (i) described below with an unsaturated silane modifier.

[0069] Here, the unmodified hydrogenated block copolymer composition (i) contains an unmodified hydrogenated block copolymer (a) represented by the following general formula (a) and an unmodified hydrogenated block copolymer (b) represented by the following general formula (b): Ar1 a -HD a -Ar2 a (a) Ar1 b -HD b -Ar2 b (b) (In the general formula (a) and the general formula (b), Ar1 a , Ar2 a , Ar1 b , and Ar2 b is an aromatic vinyl polymer block, and HD a and HD b is a hydrogenated polymer block of a conjugated diene polymer that does not contain a silane-containing functional group, and Ar1 a Weight average molecular weight (Mw(Ar1 a )) for Ar2 a Weight average molecular weight (Mw(Ar2 a )) ratio (Mw(Ar2 a ) / Mw(Ar1 a )) is 3.0 to 20, and Ar1 b Weight average molecular weight (Mw(Ar1b )) for Ar2 b Weight average molecular weight (Mw(Ar2 b )) ratio (Mw(Ar2 b ) / Mw(Ar1 b )) is 0.95 to 1.05.

[0070] Here, when the unmodified hydrogenated block copolymer composition (i) is modified with an unsaturated silane modifier, the hydrogenated polymer blocks (HD) of each conjugated diene polymer in the unmodified hydrogenated block copolymer composition (i) are usually a and HD b The carbon atoms in the hydroxyl group and the unsaturated silane modifier act to form the hydrogenated polymer block (HD) of the conjugated diene polymer. a and HD b In this case, the silane-modified hydrogenated block copolymer (I) is obtained by introducing the silane-containing functional group into the hydrogenated polymer block (HD) of the conjugated diene polymer. a and HD b ) as a side chain.

[0071] The silane-modified hydrogenated block copolymer composition (I) contains a silane-modified hydrogenated block copolymer (A-Si) having a silane-containing functional group, which is obtained by modifying an unmodified hydrogenated block copolymer (a) with an unsaturated silane modifier, and a silane-modified hydrogenated block copolymer (B-Si) having a silane-containing functional group, which is obtained by modifying an unmodified hydrogenated block copolymer (b) with an unsaturated silane modifier. The silane-modified hydrogenated block copolymer (A-Si) corresponds to the hydrogenated block copolymer (A) used in the present invention, and the silane-modified hydrogenated block copolymer (B-Si) corresponds to the hydrogenated block copolymer (B) used in the present invention.

[0072] Aromatic vinyl polymer block Ar1 constituting the unmodified hydrogenated block copolymer (a) and the unmodified hydrogenated block copolymer (b) a , Ar2 a , Ar1 b , and Ar2 bThe preferred ranges of the monomer composition, weight average molecular weight, weight average molecular weight ratio, and content of aromatic vinyl monomer unit are determined by the aromatic vinyl polymer block Ar1 constituting the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B). A , Ar2 A , Ar1 B , and Ar2 B It is preferable that the range is the same as the preferred range in

[0073] Hydrogenated block HD polymer of conjugated diene polymer a and HD b The monomers used to form the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) include hydrogenated block copolymer (HD) of a conjugated diene polymer. A and HD B Examples of the monomers used to form the copolymer include the above-mentioned monomers.

[0074] Hydrogenated block HD polymer of conjugated diene polymer a and HD b Preferred types of monomers used to form the block HD of hydrogenated conjugated diene polymer, preferred contents of each monomer unit, and a and HD b The preferred range of the vinyl bond content before hydrogenation is the hydrogenated polymer block HD of the conjugated diene polymer constituting the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B). A and HD B It is preferable that the range is the same as the preferred range in

[0075] In the unmodified hydrogenated block copolymer (a), the hydrogenated polymer block HD of the conjugated diene polymer a Weight average molecular weight (Mw(HD a )) is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, even more preferably 15,000 to 150,000, and particularly preferably 20,000 to 80,000.

[0076] The weight average molecular weight of the unmodified hydrogenated block copolymer (a) is not particularly limited, but is preferably 20,000 to 500,000, more preferably 25,000 to 300,000, and even more preferably 30,000 to 150,000.

[0077] By setting the weight average molecular weight of the unmodified hydrogenated block copolymer (a) and the weight average molecular weight of each polymer block within the above ranges, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0078] The content of aromatic vinyl monomer units relative to all monomer units in the unmodified hydrogenated block copolymer (a) is not particularly limited, but is preferably 20 to 90% by weight, more preferably 30 to 90% by weight, even more preferably 40 to 85% by weight, and particularly preferably 45 to 85% by weight. By setting the content of aromatic vinyl monomer units within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0079] In the unmodified hydrogenated block copolymer (b), the hydrogenated polymer block HD of the conjugated diene polymer b Weight average molecular weight (Mw(HD b )) is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, even more preferably 15,000 to 150,000, and particularly preferably 20,000 to 80,000.

[0080] Hydrogenated block HD polymer of conjugated diene polymer b Weight average molecular weight (Mw(HD b ) is a hydrogenated polymer block HD of a conjugated diene polymer that constitutes the hydrogenated block copolymer (A). a Weight average molecular weight (Mw(HD a )) may be equal to or different from, but it is more preferable that they are substantially equal. For example, HD a Weight average molecular weight (Mw(HD a )) against HD b Weight average molecular weight (Mw(HD b)) ratio (Mw(HD b ) / Mw(HD a )) is preferably in the range of 0.95 to 1.05.

[0081] The weight average molecular weight of the unmodified hydrogenated block copolymer (b) as a whole is not particularly limited, but is preferably 20,000 to 500,000, more preferably 25,000 to 300,000, and even more preferably 30,000 to 150,000.

[0082] By setting the weight average molecular weight of the unmodified hydrogenated block copolymer (b) and the weight average molecular weight of each polymer block within the above ranges, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0083] The content of aromatic vinyl monomer units relative to the total monomer units of the unmodified hydrogenated block copolymer (b) is not particularly limited, but is preferably 7 to 60% by weight, more preferably 10 to 50% by weight, and even more preferably 15 to 40% by weight. By setting the content of aromatic vinyl monomer units within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0084] When a production method using a coupling agent is adopted in producing the unmodified hydrogenated block copolymer composition (i), the hydrogenated polymer block of the conjugated diene polymer (for example, HD b ) may contain a residue of a coupling agent. Specifically, the hydrogenated block copolymer (B) may be a compound represented by the following formula: Ar1 b -(HD b’ -X-HD b’’ )-Ar2 b

[0085] That is, as shown in the above formula, the hydrogenated polymer block HD of the conjugated diene polymer b However, HD is reacted with the coupling agent residue X. b’ , HD b’’The residue X of the coupling agent may be a residue of a bifunctional coupling agent, which will be described later.

[0086] The molecular weight distributions of the unmodified hydrogenated block copolymer (a) and the unmodified hydrogenated block copolymer (b), and of each polymer block constituting them, which are expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) [(Mw) / (Mn)], are not particularly limited, but are each preferably 1.1 or less, more preferably 1.05 or less.

[0087] The unmodified hydrogenated block copolymer composition (i) may, for example, contain only the unmodified hydrogenated block copolymer (a) and the unmodified hydrogenated block copolymer (b) as polymer components.

[0088] The weight ratio (a / b) of the unmodified hydrogenated block copolymer (a) to the unmodified hydrogenated block copolymer (b) in the unmodified hydrogenated block copolymer composition (i) is not particularly limited, but is preferably 10 / 90 to 80 / 20, more preferably 20 / 80 to 60 / 40, and even more preferably 25 / 75 to 50 / 50. By setting the weight ratio (a / b) within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved. The weight ratio (a / b) can be determined from the area ratio of the peaks corresponding to each block copolymer in a chart obtained by high-performance liquid chromatography.

[0089] The hydrogenation rate of the olefin in the unmodified hydrogenated block copolymer composition (i) is preferably 10 to 100%, more preferably 50 to 100%, even more preferably 80 to 100%, particularly preferably 90 to 100%, and most preferably 95 to 100%. By setting the hydrogenation rate of the olefin within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0090] The weight-average molecular weight of all the polymer components constituting the unmodified hydrogenated block copolymer composition (i) is not particularly limited, but is preferably 20,000 to 500,000, more preferably 30,000 to 400,000, even more preferably 35,000 to 150,000, and particularly preferably 40,000 to 100,000. By setting the weight-average molecular weight within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0091] The molecular weight distribution, which is expressed as the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of all the polymer components constituting the unmodified hydrogenated block copolymer composition (i), is not particularly limited, but is preferably 1 to 2, more preferably 1.001 to 1.5, and even more preferably 1.01 to 1.15.

[0092] The proportion of aromatic vinyl monomer units relative to the total polymer components in the unmodified hydrogenated block copolymer composition (i) (total monomer units constituting the polymer components) is not particularly limited, but is preferably 10 to 90% by weight, more preferably 15 to 75% by weight, and even more preferably 20 to 60% by weight. By setting the proportion within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved. The above proportion is determined by using deuterated chloroform as a solvent. 1 It can be determined by H-NMR measurement.

[0093] In addition, when all polymer components constituting the hydrogenated block copolymer composition are composed only of aromatic vinyl monomer units and conjugated diene monomer units, the polymer components in the hydrogenated block copolymer composition can be decomposed by ozonolysis and then reduced with lithium aluminum hydride according to the method described in Rubber Chem. Technol., 45, 1295 (1972). This decomposes the conjugated diene monomer unit portions (including hydrogenated portions), allowing only the aromatic vinyl monomer unit portions to be isolated, thereby easily measuring the total aromatic vinyl monomer unit content. The aromatic vinyl monomer unit content and conjugated diene monomer unit content in each block copolymer can be determined by a similar method.

[0094] (Method for producing hydrogenated block copolymer composition) The method for producing the hydrogenated block copolymer composition used in the present invention is not particularly limited, and can be, for example, produced separately from the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) according to conventional block copolymer production methods and hydrogenation methods, and then blended with other polymer components and various additives as necessary, followed by mixing them according to conventional methods such as kneading, solution mixing, etc. On the other hand, in the present invention, the production method described below is preferred from the viewpoint of being able to produce the hydrogenated block copolymer composition with high productivity.

[0095] That is, the method for producing the hydrogenated block copolymer composition used in the present invention is preferably a production method comprising the following steps (1) to (7). (1): A step of polymerizing an aromatic vinyl monomer in a solvent using a polymerization initiator to obtain a solution containing an aromatic vinyl polymer having an active terminal. (2): A step of adding a conjugated diene monomer to the solution containing the aromatic vinyl polymer having active terminals obtained in the step (1) above, and polymerizing the conjugated diene monomer to obtain a solution containing an aromatic vinyl-conjugated diene block copolymer having active terminals. (3): A step of adding an aromatic vinyl monomer to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active terminal obtained in the step (2) above, and polymerizing the aromatic vinyl monomer to obtain a solution containing the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active terminal. (4): A step of adding a polymerization terminator to the solution containing the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends obtained in the step (3) in an amount of less than 1 molar equivalent relative to the active ends to deactivate a portion of the active ends of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends, thereby obtaining a solution containing block copolymer (B'). (5): A step of adding an aromatic vinyl monomer to the solution containing the block copolymer (B') obtained in the step (4) above, and polymerizing the aromatic vinyl monomer to obtain a solution containing the block copolymer (B') and the block copolymer (A'). (6): A step of subjecting the solution containing the block copolymer (B') and the block copolymer (A') obtained in the step (5) to a hydrogenation reaction to obtain a solution containing the hydrogenated block copolymer (B) and the hydrogenated block copolymer (A). (7): A step of recovering a hydrogenated block copolymer composition from the solution containing the hydrogenated block copolymer (B) and the hydrogenated block copolymer (A) obtained in the step (6) above.

[0096] <Process (1)> In the method for producing this hydrogenated block copolymer composition, first, in step (1), an aromatic vinyl monomer is polymerized in a solvent using a polymerization initiator to obtain a solution containing an aromatic vinyl polymer having an active end.

[0097] The polymerization initiator may be any polymerization initiator known to have anionic polymerization activity for aromatic vinyl monomers and conjugated diene monomers, such as organic alkali metal compounds, organic alkaline earth metal compounds, and organic lanthanoid series rare earth metal compounds.

[0098] As the organic alkali metal compound, an organic lithium compound having one or more lithium atoms in the molecule is particularly preferably used. Specific examples of the organic alkali metal compound include organic monolithium compounds such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenelithium, dialkylaminolithium, diphenylaminolithium, and ditrimethylsilylaminolithium; organic dilithium compounds such as methylenedilithium, tetramethylenedilithium, hexamethylenedilithium, isoprenyldilithium, and 1,4-dilithio-ethylcyclohexane; and organic trilithium compounds such as 1,3,5-trilithiobenzene. Among these, organic monolithium compounds are particularly preferably used.

[0099] Examples of organic alkaline earth metal compounds include n-butyl magnesium bromide, n-hexyl magnesium bromide, ethoxy calcium, calcium stearate, t-butoxy strontium, ethoxy barium, isopropoxy barium, ethylmercapto barium, t-butoxy barium, phenoxy barium, diethylamino barium, barium stearate, and ethyl barium.

[0100] In addition to the above, catalysts that form a homogeneous system in an organic solvent and have living polymerizability, such as a composite catalyst comprising a lanthanoid series rare earth metal compound containing neodymium, samarium, gadolinium, etc. / alkylaluminum / alkylaluminum halide / alkylaluminum hydride, and a metallocene catalyst containing titanium, vanadium, samarium, gadolinium, etc., can also be used.

[0101] The polymerization initiators may be used singly or in combination of two or more. The amount of the polymerization initiator used is not particularly limited and may be determined depending on the target molecular weight, but is preferably 0.01 to 20 mmol, more preferably 0.05 to 15 mmol, and even more preferably 0.1 to 10 mmol per 100 g of the total monomers used in the polymerization.

[0102] The solvent used in the polymerization is not particularly limited as long as it is inert to the polymerization initiator, but examples thereof include chain hydrocarbon solvents, cyclic hydrocarbon solvents, and mixtures thereof. Examples of chain hydrocarbon solvents include chain alkanes and alkenes having 4 to 6 carbon atoms, such as n-butane, isobutane, 1-butene, isobutylene, trans-2-butene, cis-2-butene, 1-pentene, trans-2-pentene, cis-2-pentene, n-pentane, isopentane, neo-pentane, and n-hexane. Examples of cyclic hydrocarbon solvents include aromatic compounds such as benzene, toluene, and xylene; alicyclic hydrocarbon compounds such as cyclopentane and cyclohexane; and the like. These solvents may be used alone or in combination.

[0103] The amount of solvent used is not particularly limited, but is preferably an amount such that the concentration of all block copolymers in the solution after the polymerization reaction is 3 to 60% by weight, more preferably 5 to 45% by weight, and even more preferably 7 to 30% by weight.

[0104] Furthermore, when producing a hydrogenated block copolymer composition, a Lewis base compound may be added to the reaction system to control the structure of each polymer block. Examples of Lewis base compounds include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether; tertiary amines such as tetramethylethylenediamine, trimethylamine, triethylamine, pyridine, and quinuclidine; alkali metal alkoxides such as potassium t-amyl oxide and potassium t-butyl oxide; and phosphines such as triphenylphosphine. These Lewis base compounds may be used alone or in combination.

[0105] In producing the hydrogenated block copolymer composition, the timing of adding the Lewis base compound is not particularly limited and may be appropriately determined depending on the structure of the target block copolymer.

[0106] The polymerization reaction temperature is preferably 10 to 150°C, more preferably 30 to 130°C, and even more preferably 40 to 90°C, and the polymerization time is preferably within 48 hours, more preferably 0.5 to 10 hours. The polymerization pressure is not particularly limited, as long as it is within a pressure range sufficient to maintain the monomers and solvent in a liquid phase at the polymerization temperature.

[0107] By polymerizing an aromatic vinyl monomer in a solvent using a polymerization initiator under the above conditions, a solution containing an aromatic vinyl polymer having an active end can be obtained. The aromatic vinyl polymer having an active end obtained in step (1) in this manner is a solution containing an aromatic vinyl polymer block Ar1 having a relatively small weight average molecular weight of the hydrogenated block copolymer (A) constituting the hydrogenated block copolymer composition. A and aromatic vinyl polymer block Ar1 of hydrogenated block copolymer (B) B , Ar2 B Either one of (i.e., Ar1 Bor Ar2 B Therefore, the polymerization conditions in step (1), including the amount of the aromatic vinyl monomer, may be determined depending on the target weight-average molecular weight of the polymer block.

[0108] <Process (2)> Next, in step (2), a conjugated diene monomer is added to the solution containing the aromatic vinyl polymer having active ends obtained in step (1), and the conjugated diene monomer is polymerized to obtain a solution containing an aromatic vinyl-conjugated diene block copolymer having active ends.

[0109] According to step (2), by adding a conjugated diene monomer to the solution containing the aromatic vinyl polymer having active ends obtained in step (1), a conjugated diene polymer chain is formed starting from the active ends, thereby obtaining a solution containing an aromatic vinyl-conjugated diene block copolymer having active ends.

[0110] The conjugated diene polymer chain formed in step (2) (the conjugated diene block constituting the aromatic vinyl-conjugated diene block copolymer having an active end obtained in step (2)) is a hydrogenated polymer block HD of the conjugated diene polymer of the hydrogenated block copolymer (A). A and hydrogenated block copolymer (B) of conjugated diene polymer block HD B Therefore, the polymerization conditions in step (2), including the amount of the conjugated diene polymer, may be determined depending on the target weight average molecular weight of these polymer blocks (for example, the polymerization conditions may be determined within the ranges explained in step (1) above).

[0111] <Process (3)> Next, in step (3), an aromatic vinyl monomer is added to the solution containing the aromatic vinyl-conjugated diene block copolymer having active ends obtained in step (2), and the aromatic vinyl monomer is polymerized to obtain a solution containing the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends.

[0112] According to step (3), by adding an aromatic vinyl monomer to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active end obtained in step (2), an aromatic vinyl polymer chain is formed starting from the active end, thereby obtaining a solution containing the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active end.

[0113] The aromatic vinyl polymer chain formed in step (3) (the aromatic vinyl block constituting the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active end obtained in step (3)) is the aromatic vinyl polymer block Ar1 of the hydrogenated block copolymer (B). B , Ar2 B One of the two (i.e., Ar1 B or Ar2 B Among these, a block different from the block formed in step (1) is used, for example, Ar1 B When Ar2 is formed, B Therefore, the polymerization conditions in step (3), including the amount of aromatic vinyl monomer, may be determined depending on the target weight-average molecular weight of the polymer block, etc. (for example, the polymerization conditions may be determined within the ranges explained in step (1) above).

[0114] <Process (4)> Next, in step (4), a polymerization terminator is added to the solution containing the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends obtained in step (3) in an amount of less than 1 molar equivalent relative to the active ends, thereby deactivating a portion of the active ends of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends, thereby obtaining a solution containing block copolymer (B').

[0115] The block copolymer (B') obtained in the step (4) is the block copolymer before hydrogenation to obtain the hydrogenated block copolymer (B).

[0116] The polymerization terminator can react with an active terminal to deactivate the active terminal, and after reacting with one active terminal, it does not react with another active terminal. It is not particularly limited, but a compound containing no halogen atoms is preferred. Among these, a polymerization terminator that generates a metal alkoxide, a metal aryloxide, or a metal hydroxide when reacting with an active terminal is particularly preferred. Specific examples of the polymerization terminator include water; monohydric alcohols such as methanol and ethanol; and monohydric phenols such as phenol and cresol.

[0117] The amount of the polymerization terminator used may be determined depending on the ratio between the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) constituting the hydrogenated block copolymer composition, and is not particularly limited as long as it is an amount less than 1 molar equivalent relative to the active terminals of the polymer. However, the amount of the polymerization terminator used is preferably in the range of 0.18 to 0.91 molar equivalents, more preferably in the range of 0.35 to 0.80 molar equivalents, relative to the active terminals of the polymer.

[0118] As described above, according to step (4), by adding a polymerization terminator to a solution containing an aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having active ends in an amount less than 1 molar equivalent relative to the active ends, the active ends of some of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymers having active ends are deactivated, and the copolymers with deactivated active ends become the block copolymer (B') before hydrogenation for constituting the hydrogenated block copolymer (B). The remaining portion of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymers having active ends that did not react with the polymerization terminator remains unreacted in the solution, maintaining their active ends.

[0119] <Process (5)> Next, in step (5), an aromatic vinyl monomer is added to the solution containing the block copolymer (B') obtained in step (4) above, and the aromatic vinyl monomer is polymerized to obtain a solution containing the block copolymer (B') and the block copolymer (A').

[0120] According to step (5), when an aromatic vinyl monomer is added to the solution obtained in step (4), the aromatic vinyl monomer is further polymerized from the aromatic vinyl polymer chain having the active end of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active end that has remained unreacted with the polymerization terminator, thereby extending the aromatic vinyl polymer chain and producing block copolymer (A'). Note that block copolymer (A') is an aromatic vinyl-conjugated diene-aromatic vinyl block copolymer obtained by extending the aromatic vinyl polymer chain, and serves as the block copolymer before hydrogenation to obtain hydrogenated block copolymer (A).

[0121] In this case, the aromatic vinyl polymer chain extended in step (5) is the aromatic vinyl polymer block Ar2 having a relatively large weight average molecular weight of the hydrogenated block copolymer (A) constituting the hydrogenated block copolymer composition. ATherefore, the polymerization conditions in step (5), including the amount of the aromatic vinyl monomer, are determined so as to form such an aromatic vinyl polymer block Ar2. A The polymerization conditions may be determined depending on the target weight average molecular weight, etc. (for example, the polymerization conditions may be determined within the ranges explained in the above step (1)).

[0122] After the polymerization reaction is completed, if necessary, a polymerization terminator may be added to deactivate the active ends of the polymer having active ends. In this case, the polymerization terminator may be any of those described above.

[0123] <Process (6)> Next, in step (6), the solution containing the block copolymer (B') and the block copolymer (A') obtained in step (5) is subjected to a hydrogenation reaction to obtain a solution containing the hydrogenated block copolymer (B) and the hydrogenated block copolymer (A).

[0124] The method for hydrogenating a solution containing the block copolymer (B') and the block copolymer (A') is not particularly limited, but examples thereof include a method in which a solution containing the block copolymer (B') and the block copolymer (A') is brought into contact with hydrogen in the presence of a hydrogenation catalyst.

[0125] The hydrogenation catalyst is not particularly limited, but examples thereof include supported heterogeneous catalysts in which a metal such as Ni, Pt, Pd, or Ru is supported on a carrier such as carbon, silica, alumina, or diatomaceous earth; Ziegler-type catalysts that use an organic salt or acetylacetone salt of Ni, Co, Fe, Cr, or the like and a reducing agent such as organoaluminum; organic complex catalysts such as organometallic compounds of Ru, Rh, etc.; and homogeneous catalysts that use a titanocene compound and a reducing agent such as organolithium, organoaluminum, or organomagnesium; among these, Ziegler-type catalysts are preferred.

[0126] The hydrogenation reaction can be carried out according to the methods disclosed in, for example, Japanese Patent Publication Nos. 42-8704, 43-6636, Japanese Patent Laid-Open Nos. 59-133203, and 60-220147.

[0127] The hydrogenation reaction conditions may be selected depending on the desired hydrogenation rate of the olefin, and the hydrogenation reaction temperature is preferably 0 to 200°C, more preferably 30 to 150°C. The hydrogen pressure used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and even more preferably 0.3 to 5 MPa, and the hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction may be carried out by a batch process, a continuous process, or a combination thereof.

[0128] <Process (7)> Next, in step (7), the target hydrogenated block copolymer composition is recovered from the solution containing the hydrogenated block copolymer (B) and the hydrogenated block copolymer (A) obtained in step (6).

[0129] The recovery method may be any conventional method and is not particularly limited. For example, after the reaction is completed, additives such as an antioxidant may be added as needed, and then the solution may be subjected to a known solvent method such as direct drying or steam stripping, thereby recovering the target hydrogenated block copolymer composition.

[0130] When the hydrogenated block copolymer composition is recovered as a slurry by steam stripping or the like, it is preferable to dehydrate it using an arbitrary dehydrator such as an extruder-type squeezer to recover the hydrogenated block copolymer composition in the form of crumbs, and then dry the obtained crumbs using an arbitrary dryer such as a band dryer or an expansion extrusion dryer. The hydrogenated block copolymer composition thus obtained may be processed into pellets or the like according to a conventional method before use.

[0131] The solid (pellet, crumb, etc.) hydrogenated block copolymer composition thus obtained is preferably used after reducing the water content in the solid hydrogenated block copolymer composition using a dryer such as a hopper dryer, a hot air circulation tray dryer, a tray vacuum dryer, an agitation vacuum dryer, etc. The drying conditions are not particularly limited as long as the target water content can be achieved, and may be set depending on the amount of water to be reduced and the type of dryer, etc., but are usually set at a drying temperature of 40 to 90°C for a drying time of 1 to 24 hours.

[0132] According to the above-described method for producing a hydrogenated block copolymer composition, the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) can be continuously produced in the same reaction vessel, and therefore the target hydrogenated block copolymer composition can be produced with superior productivity compared to the case where each hydrogenated block copolymer is produced separately and then mixed.

[0133] In addition to the above-described preferred production method (a production method comprising steps (1) to (7)), when producing the hydrogenated block copolymer composition used in the present invention, a production method for a hydrogenated block copolymer composition comprising the following steps (1a) to (6a) is also preferably used. (1a): A step of polymerizing an aromatic vinyl monomer in a solvent using a polymerization initiator to obtain a solution containing an aromatic vinyl polymer having an active terminal. (2a): A step of adding a conjugated diene monomer to the solution containing the aromatic vinyl polymer having active terminals obtained in the above step (1a) and polymerizing the conjugated diene monomer to obtain a solution containing an aromatic vinyl-conjugated diene block copolymer having active terminals. (3a): A step of adding a bifunctional coupling agent to a solution containing the aromatic vinyl-conjugated diene block copolymer having active ends obtained in the step (2a) above, in an amount such that the total amount of functional groups relative to the active ends is less than 1 molar equivalent, thereby coupling a portion of the aromatic vinyl-conjugated diene block copolymer having active ends, thereby obtaining a solution containing block copolymer (B'). (4a): A step of adding an aromatic vinyl monomer to a solution containing the block copolymer (B') obtained in the step (3a) above, and polymerizing the aromatic vinyl monomer to obtain a solution containing the block copolymer (B') and the block copolymer (A'). (5a): A step of subjecting the solution containing the block copolymer (B') and the block copolymer (A') obtained in the step (4a) above to a hydrogenation reaction to obtain a solution containing the hydrogenated block copolymer (B) and the hydrogenated block copolymer (A). (6a): A step of recovering a hydrogenated block copolymer composition from the solution containing the hydrogenated block copolymer (B) and the hydrogenated block copolymer (A) obtained in the step (5a) above.

[0134] <Process (1a), Process (2a)> Steps (1a) and (2a) are similar to the above-mentioned steps (1) and (2), and similar conditions can be employed.

[0135] <Process (3a)> In step (3a), a bifunctional coupling agent is added to the solution containing the aromatic vinyl-conjugated diene block copolymer having active ends obtained in step (2a) in an amount such that the total amount of functional groups relative to the active ends is less than 1 molar equivalent, thereby coupling a portion of the aromatic vinyl-conjugated diene block copolymer having active ends to obtain a solution containing block copolymer (B').

[0136] The block copolymer (B') obtained in the step (3a) is the block copolymer before hydrogenation to obtain the hydrogenated block copolymer (B).

[0137] The bifunctional coupling agent is not particularly limited as long as it has two functional groups that react with the active terminal, and examples thereof include bifunctional halogenated silanes such as dichlorosilane, monomethyldichlorosilane, and dimethyldichlorosilane; bifunctional halogenated alkanes such as dichloroethane, dibromoethane, methylene chloride, and dibromomethane; and bifunctional tin halides such as dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin, diethyldichlorotin, monobutyldichlorotin, and dibutyldichlorotin. The amount of the bifunctional coupling agent used may be determined depending on the ratio of the hydrogenated block copolymer (A) to the hydrogenated block copolymer (B) that constitute the hydrogenated block copolymer composition.

[0138] As described above, according to step (3a), by adding a bifunctional coupling agent to a solution containing an aromatic vinyl-conjugated diene block copolymer having active ends in an amount such that the total number of functional groups relative to the active ends is less than 1 molar equivalent, a portion of the aromatic vinyl-conjugated diene block copolymer having active ends undergoes coupling to form the block copolymer (B') before hydrogenation, which is used to form the hydrogenated block copolymer (B). The remaining portion of the aromatic vinyl-conjugated diene block copolymer having active ends that did not react with the bifunctional coupling agent remains unreacted in the solution, maintaining its active ends.

[0139] <Process (4a)> Next, in step (4a), an aromatic vinyl monomer is added to the solution containing the block copolymer (B') obtained in step (3a) above, and the aromatic vinyl monomer is polymerized to obtain a solution containing the block copolymer (B') and the block copolymer (A').

[0140] According to step (4a), when an aromatic vinyl monomer is added to the solution obtained in step (3a), the aromatic vinyl monomer is polymerized from the active ends of the aromatic vinyl-conjugated diene block copolymer having active ends that remain unreacted with the bifunctional coupling agent to form an aromatic vinyl polymer chain, thereby obtaining block copolymer (A'). Note that block copolymer (A') is the block copolymer before hydrogenation to obtain hydrogenated block copolymer (A).

[0141] At this time, the aromatic vinyl polymer chain formed in step (4a) is a hydrogenated block copolymer composition, and the aromatic vinyl polymer block Ar2 having a relatively large weight average molecular weight of the hydrogenated block copolymer (A) is A Therefore, the polymerization conditions in step (4a), including the amount of the aromatic vinyl monomer, are determined so as to form such an aromatic vinyl polymer block Ar2. A The polymerization conditions may be determined depending on the target weight average molecular weight, etc. (for example, the polymerization conditions may be determined within the ranges explained in the above step (1)).

[0142] After the polymerization reaction is completed, if necessary, a polymerization terminator may be added to deactivate the active ends of the polymer having active ends. In this case, the polymerization terminator may be any of those described above.

[0143] <Process (5a), Process (6a)> The solution containing block copolymer (B') and block copolymer (A') obtained in step (4a) can be used to obtain the hydrogenated block copolymer composition used in the present invention through the operations in steps (5a) and (6a) described above. Note that steps (5a) and (6a) are similar to steps (6) and (7) described above, and similar conditions can be used for these steps.

[0144] When at least a part of the hydrogenated block copolymer constituting the hydrogenated block copolymer composition used in the present invention has a silane-containing functional group, the method for producing the hydrogenated block copolymer composition used in the present invention preferably further comprises a modification step for introducing the silane-containing functional group.

[0145] For example, when the hydrogenated block copolymer composition used in the present invention is the above-mentioned silane-modified hydrogenated block copolymer composition (I), the silane-modified hydrogenated block copolymer composition (I) is preferably produced by a production method including a step of obtaining an unmodified hydrogenated block copolymer composition (i) and a modification step of reacting the unmodified hydrogenated block copolymer composition (i) with an unsaturated silane modifier. This production method is described below.

[0146] In the step of obtaining the unmodified hydrogenated block copolymer composition (i), the method for obtaining the unmodified hydrogenated block copolymer composition (i) is not particularly limited, but it is preferable to obtain the unmodified hydrogenated block copolymer composition (i) in the same manner as the production method including the above-mentioned steps (1) to (7). Alternatively, the unmodified hydrogenated block copolymer composition (i) can also be obtained in the same manner as the production method including the above-mentioned steps (1a) to (6a).

[0147] In the modification step, the method for reacting the unmodified hydrogenated block copolymer composition (i) with the unsaturated silane modifier is not particularly limited, but a method in which the unmodified hydrogenated block copolymer composition (i), the unsaturated silane modifier, and a peroxide are melt-kneaded is preferred.

[0148] The unsaturated silane modifier may be used alone or in combination of two or more. The amount of the unsaturated silane modifier used is not particularly limited, but is preferably 0.1 to 20 g, more preferably 0.5 to 15 g, and even more preferably 1 to 10 g per 100 g of the polymer component to be modified with the unsaturated silane modifier.

[0149] Examples of peroxides include organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-t-butylperoxyhexane, 2,5-dimethyl-t-butylperoxyhexyne, 1,3-bis(t-butylperoxyisopropyl)benzene, p-chlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, t-butylbenzoate, and 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane. These can be used alone or in combination of two or more.

[0150] The amount of peroxide used is not particularly limited, but is preferably 0.01 to 1 g, more preferably 0.02 to 0.5 g, and even more preferably 0.05 to 0.2 g per 1 g of the unsaturated silane modifier used.

[0151] The method for melt-kneading the unmodified hydrogenated block copolymer composition (i), the unsaturated silane modifier, and the peroxide is not particularly limited, and examples thereof include a method in which the components are heated, melt-mixed using a kneading device such as a roll, a Banbury mixer, a kneader, a Labo Plastomill, a single-screw extruder, or a twin-screw extruder. The conditions for the heated, melt-mixed components are preferably those that can prevent excessive decomposition of the components or the progression of unexpected reactions. For example, the mixing temperature is preferably 180 to 260°C, more preferably 200 to 240°C. The mixing time is preferably 0.5 to 20 minutes, more preferably 1 to 10 minutes.

[0152] The unmodified hydrogenated block copolymer composition (i), the unsaturated silane modifier, and the peroxide may be melt-kneaded, and then the resulting mixture may be mixed with a condensation reaction catalyst for condensing the silane-containing functional groups. This allows for the introduction of crosslinked structures derived from the silane-containing functional groups between some of the polymer chains constituting the silane-modified hydrogenated block copolymer composition (I), thereby achieving partial crosslinking.

[0153] The crosslinked structure derived from the silane-containing functional group preferably contains an -Si-O-Si- bond. For example, when an unsaturated silane modifier having an alkoxy group is used as the unsaturated silane modifier and a condensation reaction catalyst is further used, a crosslinked structure containing an -Si-O-Si- bond is introduced between some of the polymer chains constituting the silane-modified hydrogenated block copolymer composition (I).

[0154] Examples of condensation reaction catalysts include polycarboxylic acids such as maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, trimellitic acid, pyromellitic acid, and acid anhydrides thereof; sulfonic acids such as paratoluenesulfonic acid; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, and didecyl phosphate. phosphoric acids or phosphoric acid esters such as propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, allyl glycidyl ether, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, Cardura E, Epicoat 828, Epicoat 1001 manufactured by Yuka Shell Epoxy Co., Ltd., and other epoxy compounds with phosphoric acid and / or acid monoesters Adducts with phosphate esters; titanium compounds such as titanium acetylacetonate, isopropyl tristearoyl titanate, tetraisopropyl bis(dioctyl phosphite) titanate, and bis(dioctyl pyrophosphate) oxyacetate titanate; tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, dibutyltin thioglycolate, dibutyltin diacetylacetonate, dioctyltin dilaurate, dioctyltin maleate, and tin octylate; aluminum isoprene Examples of suitable alkoxy compounds include aluminum compounds such as tetra-n-butoxyzirconium, zirconium octylate, and reaction products of alkoxyzirconium with acetylacetone or acetoacetic ester; amines such as hexylamine, di-2-ethylhexylamine, and N,N-dimethyldodecylamine; and alkaline compounds such as sodium hydroxide and potassium hydroxide.As the condensation reaction catalyst, a mixture or reaction product of an acidic organic compound and a basic compound can also be used.

[0155] Among these, polycarboxylic acids, titanium compounds, and tin compounds are preferred, and succinic acid, titanium acetylacetonate, and dibutyltin dilaurate are more preferred.

[0156] The amount of the condensation reaction catalyst used is not particularly limited, but is preferably 0.1 to 10 g, more preferably 0.2 to 5 g, per 100 g of the unmodified hydrogenated block copolymer composition (i).

[0157] The method for mixing the mixture of the unmodified hydrogenated block copolymer composition (i), the unsaturated silane modifier, and the peroxide with the condensation reaction catalyst is not particularly limited. Examples include a method in which the components are heated and melted and mixed using a kneading device such as a roll, a Banbury mixer, a kneader, a Labo Plastomill, a single-screw extruder, or a twin-screw extruder, or a method in which the components are dissolved in a solvent and mixed uniformly, and then the solvent is removed by heating or other methods. Among these, the heated and melted mixing method is preferred from the viewpoint of more efficient mixing. The conditions for the heated and melted mixing are preferably those that can prevent excessive decomposition of the components or the progression of unexpected reactions. For example, the mixing temperature is preferably 180 to 260°C, more preferably 200 to 240°C. The mixing time is preferably 0.5 to 20 minutes, more preferably 1 to 10 minutes.

[0158] It is also preferable to carry out consecutively the modification step of melt-kneading the unmodified hydrogenated block copolymer composition (i), the unsaturated silane modifier, and the peroxide to obtain a mixture, and the crosslinking step of mixing the resulting mixture with a condensation reaction catalyst for condensing the silane-containing functional groups. This method allows for high productivity of crosslinking while suppressing excessive decomposition of each component or the progression of unexpected reactions. In this production method, the modification reaction and the crosslinking reaction may proceed simultaneously after the addition of the condensation reaction catalyst.

[0159] <Epoxy resin (C)> The epoxy resin composition of the present invention contains an epoxy resin (C). In the present invention, the epoxy resin (C) used is preferably one that is liquid at room temperature to 100° C. The epoxy resin (C) may be used alone or in combination of two or more.

[0160] Examples of the epoxy resin (C) used in the present invention include diglycidyl ethers based on bisphenol A, bisphenol F, or resorcinol; polyglycidyl ethers of phenol novolac resins or cresol novolac resins; diglycidyl ethers of hydrogenated bisphenol A; glycidylamine-type resins; linear aliphatic epoxide-type resins; diglycidyl esters of phthalic acid, hexahydrophthalic acid, or tetrahydrophthalic acid. Modified epoxy resins such as ethylene oxide- or propylene oxide-added bisphenol A-type epoxy resins, dimer acid-type epoxy resins, and epoxy-modified NBR can also be used.

[0161] The epoxy equivalent of the epoxy resin (C) is not particularly limited, but is preferably 100-500, and more preferably 120-300.

[0162] <Curing agent (D)> The epoxy resin composition of the present invention contains a curing agent (D). In the present invention, the curing agent (D) undergoes a crosslinking reaction with the epoxy groups of the epoxy resin (C) and has the effect of curing the epoxy resin (C). The curing agent (D) may be used alone or in combination of two or more.

[0163] The curing agent (D) may be any known curing agent for epoxy resins. Specific examples include dicyandiamide, 4,4'-diaminodiphenyl sulfone, imidazole derivatives such as 2-n-heptadecylimidazole, isophthalic dihydrazide, N,N-dialkylurea derivatives, N,N-dialkylthiourea derivatives, acid anhydrides such as tetrahydrophthalic anhydride, polyamines such as isophoronediamine, m-phenylenediamine, ethylenediamine, hexamethylenediamine, m-xylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, aminoalkyl cyclic compounds such as bis(aminomethyl)cyclohexane, N-aminoethylpiperazine, trisdimethylaminomethylphenol, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, melamine, boron trifluoride complex compounds, and polyamidoamines formed from adducts of various dimer acids and diamines. Among these, amine compounds such as polyamines and polyamidoamines are preferred.

[0164] The contents of the epoxy resin (C) and curing agent (D) in the epoxy resin composition of the present invention are not particularly limited. For example, the weight ratio ((C+D) / (A+B)) of the total content of the epoxy resin (C) and curing agent (D) to the total content of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) is preferably 99 / 1 to 70 / 30, more preferably 97 / 3 to 74 / 26, and even more preferably 95 / 5 to 78 / 22. By setting the weight ratio ((C+D) / (A+B)) within the above range, the adhesiveness and impact absorption properties of the epoxy resin composition can be further improved.

[0165] Furthermore, when even better adhesion is required, the weight ratio ((C+D) / (A+B)) is preferably 99 / 1 to 80 / 20, more preferably 97 / 3 to 82 / 18, and even more preferably 95 / 5 to 85 / 15.

[0166] (Other ingredients) The epoxy resin composition of the present invention may contain polymer components other than the hydrogenated block copolymer composition, or may contain only the hydrogenated block copolymer composition as a polymer component, as long as the effects of the present invention are not impaired.

[0167] Examples of other polymer components include unhydrogenated aromatic vinyl-conjugated diene-aromatic vinyl block copolymers, aromatic vinyl-conjugated diene block copolymers, aromatic vinyl homopolymers, conjugated diene homopolymers, aromatic vinyl-conjugated diene random copolymers, and branched polymers thereof; thermoplastic elastomers such as polyolefin-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyester-based thermoplastic elastomers; thermoplastic resins such as polyvinyl chloride, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, and polyphenylene ether; etc. These may be used alone or in combination of two or more.

[0168] In the epoxy resin composition of the present invention, the content of polymer components other than the hydrogenated block copolymer composition is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight, even more preferably 0 to 5 parts by weight, particularly preferably 0 to 1 part by weight, and most preferably substantially 0 part by weight, relative to 100 parts by mass of the hydrogenated block copolymer composition.

[0169] The epoxy resin composition of the present invention may further contain, as necessary, an antioxidant, zinc oxide, a filler, a softener, an antibacterial agent, a light stabilizer, an ultraviolet absorber, a dye, a lubricant, and the like.

[0170] The epoxy resin composition of the present invention can be produced, for example, by mixing the hydrogenated block copolymer composition, the epoxy resin (C), the curing agent (D), and other components used as needed. For example, the hydrogenated block copolymer composition, the epoxy resin (C), and other components used as needed may be mixed together, and then the curing agent (D) may be added and mixed. Alternatively, the hydrogenated block copolymer composition, the curing agent (D), and other components used as needed may be mixed together, and then the epoxy resin (C) may be added and mixed.

[0171] The method for mixing the components is not particularly limited, and examples thereof include a method in which the components are heated, melted, and mixed using a kneading device such as a roll, a Banbury mixer, a kneader, a Labo Plastomill, a single-screw extruder, or a twin-screw extruder; and a method in which the components are dissolved in a solvent and mixed uniformly, and then the solvent is removed by heating or other methods. Among these, the heated, melted, and mixed method is preferred from the viewpoint of more efficient mixing. The conditions for the heated, melted, and mixed methods are preferably those that can prevent excessive decomposition of the components and the progression of unexpected reactions. For example, the mixing temperature is preferably 100 to 200°C, more preferably 120 to 180°C. The mixing time is preferably 0.5 to 60 minutes, more preferably 1 to 20 minutes.

[0172] In the epoxy resin composition of the present invention, the hydrogenated block copolymer composition and the epoxy resin (C) may be partially cured or crosslinked. In addition, in the epoxy resin composition of the present invention, at least a portion of the curing agent (D) may react with the epoxy resin (C), and the curing agent (D) may be present in a state of being bound to the epoxy resin (C).

[0173] The epoxy resin composition of the present invention may be molded into a desired shape depending on the application. Furthermore, the molded epoxy resin composition may be heated as needed to promote the curing reaction.

[0174] <Application> The epoxy resin composition of the present invention has excellent adhesion and impact absorption properties to a wide range of materials. Therefore, the epoxy resin composition of the present invention can be suitably used in a variety of applications, such as impact absorbing materials such as reinforced plastics (e.g., CFRP) used in aircraft, wind turbine covering materials, adhesives for electronic substrates (power module systems), structural adhesives for automobiles, structural adhesives for aircraft, structural adhesives for sports components, and interlayer films for bulletproof vests. Furthermore, cured products obtained by curing the epoxy resin composition of the present invention may also be used in the above applications.

[0175] In particular, the epoxy resin composition of the present invention can be suitably used as an adhesive for bonding dissimilar materials. For example, it can be suitably used as an adhesive for bonding materials such as glass, silicon wafers, ceramics, metals, plastics, reinforcing fibers, wood, leather, stone, concrete, rock, paper, corrugated cardboard, fabric, glass, brick, plaster, cement, tiles, mortar, and asphalt. Furthermore, because the epoxy resin composition of the present invention has excellent impact absorption properties, when dissimilar materials are bonded using the epoxy resin composition of the present invention, the resulting bonded body has excellent impact resistance. [Example]

[0176] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Note that "parts" and "%" are by weight unless otherwise specified. The test methods used in these examples and comparative examples are as follows.

[0177] [Weight-average molecular weight and molecular weight distribution of (hydrogenated) block copolymers] A chart based on the molecular weight in terms of polystyrene was obtained by high-performance liquid chromatography using tetrahydrofuran as a carrier at a flow rate of 0.35 ml / min. The weight-average molecular weight and molecular weight distribution of the (hydrogenated) block copolymer were determined based on the chart obtained. The analyzer used was a Tosoh HLC8320, and the column consisted of three connected Shodex® KF-404HQ columns manufactured by Showa Denko (column temperature: 40°C). The detectors used were a differential refractometer and an ultraviolet detector. Molecular weight calibration was performed using 12 standard polystyrenes (5 to 3 million) manufactured by Polymer Laboratory.

[0178] [Weight ratio of each polymer] The weight ratio of each polymer was determined from the area ratio of the peak corresponding to each polymer in the chart obtained by the above high performance liquid chromatography.

[0179] [Weight average molecular weight of styrene polymer block of each block copolymer] According to the method described in Rubber Chem. Technol., 45, 1295 (1972), the isoprene polymer block of the (hydrogenated) block copolymer was decomposed by reacting the (hydrogenated) block copolymer with ozone and reducing it with lithium aluminum hydride.

[0180] Specifically, the procedure was as follows: 300 mg of sample was dissolved in a reaction vessel containing 100 ml of molecular sieve-treated dichloromethane. The reaction vessel was then placed in a cooling bath and cooled to -25°C. Ozone generated by an ozone generator was then introduced into the reaction vessel while oxygen was flowing at a rate of 170 ml / min. Thirty minutes after the start of the reaction, completion of the reaction was confirmed by introducing the gas flowing out of the reaction vessel into an aqueous potassium iodide solution. Next, 50 ml of diethyl ether and 470 mg of lithium aluminum hydride were placed in a separate reaction vessel purged with nitrogen. While the reaction vessel was cooled with ice water, the ozone-reacted solution was slowly added dropwise to the reaction vessel. The reaction vessel was then placed in a water bath, gradually heated, and refluxed at 40°C for 30 minutes. While stirring the solution, dilute hydrochloric acid was gradually added dropwise to the reaction vessel until hydrogen generation was almost completely eliminated. After the reaction, the solid product formed in the solution was filtered and extracted with 100 ml of diethyl ether for 10 minutes. This extract and the filtrate were combined, and the solvent was distilled off to obtain a solid sample. The weight-average molecular weight of the sample thus obtained was measured according to the above-mentioned method for measuring weight-average molecular weight, and the value was taken as the weight-average molecular weight of the styrene polymer block.

[0181] [Weight average molecular weight of the (hydrogenated) isoprene polymer block of each block copolymer] The weight average molecular weight of the corresponding styrene polymer block was subtracted from the weight average molecular weight of each polymer determined as described above, and the weight average molecular weight of the (hydrogenated) isoprene polymer block was determined based on the calculated value.

[0182] [Vinyl bond content of isoprene polymer block (before hydrogenation)] Deuterated chloroform was used as the solvent. 1 It was determined based on H-NMR measurement.

[0183] [Styrene unit content of each block copolymer] The styrene content was determined based on the ratio of the detected intensities measured by the differential refractometer and the ultraviolet detector in the high performance liquid chromatography. Copolymers having different styrene unit contents were prepared in advance, and a calibration curve was created using these copolymers.

[0184] [Styrene unit content of (hydrogenated) block copolymer] Deuterated chloroform was used as the solvent. 1 The styrene unit content of the (hydrogenated) block copolymer was determined based on the H-NMR measurement.

[0185] [Olefin hydrogenation rate (mol%) of hydrogenated block copolymer] Deuterated chloroform was used as the solvent. 1 The olefin amount was determined for each of the block copolymer before hydrogenation and the hydrogenated block copolymer after hydrogenation by H-NMR spectrum measurement, and the olefin hydrogenation rate (mol %) was calculated based on the difference in the olefin amount before and after hydrogenation. 1 In the H-NMR spectrum measurement, deuterated chloroform was used as the solvent, and a JMN-AL series AL400 (manufactured by JEOL) was used as the NMR measurement device. In the present examples and comparative examples, both the block copolymer before hydrogenation and the hydrogenated block copolymer after hydrogenation contained only isoprene units as olefin-derived monomer units, so the hydrogenation rate of isoprene was determined in the measurement, and this was taken as the olefin hydrogenation rate.

[0186] [Shore A Hardness of Hydrogenated Block Copolymer Composition] The Shore A hardness of the hydrogenated block copolymer composition was determined in accordance with ISO 7619.

[0187] [Adhesiveness] An epoxy resin composition was used to bond a 100 mm long x 25 mm wide CFRP sheet (a JIS K6850 matte CFRP test specimen manufactured by Standard Test Piece Co., Ltd.) to the ends of a 100 mm long x 25 mm wide aluminum sheet (a 12.5 mm long x 25 mm wide area at the longitudinal end) to prepare an adhesion sample measuring approximately 187.5 mm long x 25 mm wide. Specifically, the epoxy resin composition was applied to one end of the CFRP sheet (a 12.5 mm long x 25 mm wide area at the longitudinal end) to a thickness of 0.25 mm. The end of the aluminum sheet was then placed on top of the epoxy resin composition so that the CFRP sheet and the aluminum sheet did not come into direct contact. The resulting sample was placed in a pressure autoclave and maintained at 100°C, 0.8 MPa, and 2 hours to prepare an adhesion sample. The tensile shear bond strength of the bonded samples was measured in accordance with JIS K6850 using a precision universal testing machine (product name "Autograph AG-10kN X plus", manufactured by Shimadzu Corporation) at a test temperature of 23°C and a test speed of 1 mm / min. If the tensile shear bond strength is 5 MPa or higher, it can be determined that the epoxy resin composition has excellent adhesive properties to a wide range of materials. Furthermore, if the tensile shear bond strength is even greater, it can be determined that the adhesive properties of the epoxy resin composition are even better.

[0188] [Shock absorption] A sheet of the epoxy resin composition molded to a length of 25 mm, width of 25 mm, and thickness of 1 mm was placed at the center of a CFRP sheet (a CFRP (matt) evaluation specimen for JIS K6850 adhesion testing, manufactured by Standard Test Piece Co., Ltd.), and the epoxy resin composition sheet and the CFRP sheet were closely attached. This was placed in a pressurized autoclave and held at 100°C, 0.8 MPa, and 2 hours to prepare a sample. A drop weight test was conducted in which a weight equipped with an acceleration sensor was dropped onto the center of the sample from a height of 100 mm. The maximum acceleration recorded in the acceleration-time diagram for each drop weight test was determined and used as the drop impact acceleration (X1) for this test. The drop weight test was also conducted in the same manner except that a CFRP sheet alone was used instead of the sample, and the drop impact acceleration (X0) was determined. The percentage reduction in drop impact acceleration (X1) when the sample was used (1-X1 / X0) was calculated based on the drop impact acceleration (X0) when the CFRP sheet alone was used. The greater the reduction rate of the drop impact acceleration, the more excellent the impact absorption of the epoxy resin composition can be determined.

[0189] The detailed conditions for the drop weight test are shown below. Test room temperature: 23±2℃ Falling object tip shape: Made of SUS, R10 hemisphere shape Weight of the falling object: Approximately 4 kg Drop height: Approx. 10 cm Acceleration measurement sensor: PCB Piezotronics Model: M350B04 Acceleration recorder: OROS FFT analyzer, model: OR35-4 Small compression type load cell: Kyowa Dengyo Model: LCX-A-10kN-ID

[0190] [Production Example 1] (1) Preparation of Block Copolymer Composition Before Hydrogenation A pressure reactor was charged with 56.6 kg of cyclohexane, 387 mmol of dibutyl ether, and 1.23 kg of styrene. While stirring the entire contents at 50°C, 208 mmol of n-butyllithium (1.6 M solution) was added. After the addition was completed, the temperature was raised to 55°C and polymerization reaction was carried out for 1 hour (first stage polymerization). The polymerization conversion of styrene at this time was 100%.

[0191] Subsequently, 5.00 kg of isoprene was continuously added to the reactor over 1 hour while controlling the temperature to maintain a temperature of 50 to 60°C. After the addition of isoprene was completed, the polymerization reaction was carried out for another 1 hour (second polymerization stage). The polymerization conversion of isoprene at this time was 100%.

[0192] Next, 1.23 kg of styrene was added continuously over 1 hour while controlling the temperature to maintain 50-60°C. After the addition of styrene was completed, the polymerization reaction was continued for another hour to obtain a solution containing a styrene-isoprene-styrene triblock copolymer with active terminals (third polymerization stage). The polymerization conversion of styrene at this time was 100%.

[0193] Next, 145 mmol of methanol was added as a polymerization terminator, and the mixture was mixed to deactivate some of the active ends of the styrene-isoprene-styrene triblock copolymer having active ends, thereby obtaining a solution containing a styrene-isoprene-styrene triblock copolymer that would become block copolymer (B') for obtaining hydrogenated block copolymer (B).

[0194] Thereafter, 2.53 kg of styrene was continuously added over 1 hour while maintaining the temperature at 50-60°C. After the addition of styrene was completed, the polymerization reaction was continued for another hour to obtain a solution containing a styrene-isoprene-styrene triblock copolymer having active terminals, which would become the block copolymer (A') for obtaining the hydrogenated block copolymer (A) (fourth polymerization stage). The polymerization conversion of styrene at this time was 100%.

[0195] Finally, 271 mmol of methanol was added as a polymerization terminator and mixed to deactivate all of the active ends of the styrene-isoprene-styrene triblock copolymer, thereby completing the polymerization reaction. The amounts of each reagent used in the reaction are summarized in Table 1.

[0196] (2) Hydrogenation reaction of the block copolymer composition before hydrogenation The solution containing the block copolymer composition before hydrogenation obtained above was subjected to a hydrogenation reaction to obtain a solution containing a hydrogenated block copolymer composition. The hydrogenation reaction was carried out by adding Ni(AcAc)2-TIBAL catalyst as a hydrogenation catalyst to the solution containing the block copolymer composition before hydrogenation obtained above in a ratio of 0.5% based on the block copolymer composition before hydrogenation, under conditions of a hydrogen pressure of 3 MPa, a reaction temperature of 80°C, and a reaction time of 3 hours. A portion of the solution containing the hydrogenated block copolymer composition thus obtained was removed and measured according to the method described above. The results are shown in Table 2.

[0197] (3) Recovery of hydrogenated block copolymer composition 0.3 parts of 2,6-di-t-butyl-p-cresol as an antioxidant was added to 100 parts of the solution containing the hydrogenated block copolymer composition obtained as described above and mixed. The mixed solution was added dropwise in small amounts to warm water heated to 85-95°C to volatilize the solvent, yielding a precipitate. The resulting precipitate was crushed and dried with hot air at 85°C to recover a crumb-like hydrogenated block copolymer composition. The crumb-like hydrogenated block copolymer composition was fed into a single-screw extruder equipped with an underwater hot cut device at the tip of the extruder and formed into cylindrical pellets with an average diameter of approximately 5 mm and an average length of approximately 5 mm. The pellets were placed in a hopper dryer heated to 60°C and dried for 10 hours while circulating dry air at 60°C to obtain a hydrogenated block copolymer composition (Polymer 1) containing hydrogenated block copolymer (A) and hydrogenated block copolymer (B). The Shore A hardness of the hydrogenated block copolymer composition was measured according to the method described above. The results are shown in Table 2.

[0198] [Production Example 2] A hydrogenated block copolymer composition (Polymer 2) containing hydrogenated block copolymer (A) and hydrogenated block copolymer (B) was obtained in the same manner as in Production Example 1, except that the amounts of each reagent used in the reaction were changed to those shown in Table 1, and measurements were carried out in the same manner. The results are shown in Table 2.

[0199] [Production Example 3] A hydrogenated block copolymer (B) (polymer 3) was obtained in the same manner as in Production Example 1, except that the amounts of each reagent used in the reaction were changed to the amounts listed in Table 1, and measurements were similarly performed. The results are shown in Table 2. In Production Example 3, after the third polymerization stage, methanol was added as a polymerization terminator in the amount listed in Table 1 and mixed to deactivate all active ends of the styrene-isoprene-styrene triblock copolymer having active ends, thereby completing the polymerization reaction. This resulted in a solution containing the block copolymer before hydrogenation. A hydrogenated block copolymer (B) (polymer 3) was then obtained in the same manner as in Production Example 1, except that the resulting solution containing the block copolymer before hydrogenation was used, and measurements were similarly performed. The results are shown in Table 2.

[0200] [Table 1]

[0201] [Table 2]

[0202] Example 1 In Example 1, first, the hydrogenated block copolymer composition (polymer 1) obtained in Production Example 1 was used as an unmodified hydrogenated block copolymer composition (i), and a silane-modified hydrogenated block copolymer composition (I) (silane-modified polymer 1) was obtained according to the following procedure.

[0203] 100 parts of the hydrogenated block copolymer composition (polymer 1) obtained in Production Example 1, 3 parts of vinyltrimethoxysilane, and 0.25 parts of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B, manufactured by NOF Corporation, organic peroxide) were fed to a small twin-screw kneader (Xplore MC40) and melt-kneaded at 220°C for 3 minutes. This resulted in the hydrogenation of the hydrogenated polymer block HD of the hydrogenated block copolymer (a) in the hydrogenated block copolymer composition (polymer 1). a and hydrogenated block copolymer (b) hydrogenated polymer block HD b A silane-containing functional group derived from vinyltrimethoxysilane was introduced into the silane-modified hydrogenated block copolymer (A-Si). As a result, a silane-modified hydrogenated block copolymer composition (Silane-modified Polymer 1) containing the silane-modified hydrogenated block copolymer (A-Si) and the silane-modified hydrogenated block copolymer (B-Si) was obtained.

[0204] Next, an epoxy resin composition was obtained according to the following procedure. As the hydrogenated block copolymer composition, 10 parts of the silane-modified hydrogenated block copolymer composition (silane-modified polymer 1) obtained above was used. As the epoxy resin (C), an epoxy resin (trade name "SikaPower®-4720A", manufactured by Sika Japan, density 1.08 kg / L) was used. As the curing agent (D), an amine-based curing agent (trade name "SikaPower®-4720B", manufactured by Sika Japan, density 1.13 kg / L) was used. The total amount of epoxy resin (C) and curing agent (D) used was 90 parts. In all examples and comparative examples, the ratio of epoxy resin (C) to curing agent (D) used was 2:1 by volume.

[0205] The hydrogenated block copolymer composition and epoxy resin (C) were fed into a small twin-screw kneader (trade name "Xplore MC15HT", manufactured by Xplore Instruments) and melt-kneaded at 160°C for 10 minutes to obtain a mixture. The obtained mixture was quickly mixed with curing agent (D) at room temperature to obtain an epoxy resin composition. The obtained epoxy resin composition was used to evaluate its adhesion and impact absorption properties according to the methods described above. The results are shown in Table 3.

[0206] Example 2 Epoxy resin compositions were obtained in the same manner as in Example 1, except that the amounts of the hydrogenated block copolymer composition, epoxy resin (C), and curing agent (D) used were changed as shown in Table 3, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0207] Example 3 An epoxy resin composition was obtained in the same manner as in Example 1, except that the hydrogenated block copolymer composition (Polymer 1) obtained in Production Example 1 was used instead of the silane-modified hydrogenated block copolymer composition (Silane-modified Polymer 1), and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0208] Example 4 A silane-modified hydrogenated block copolymer composition (silane-modified polymer 2) containing the silane-modified hydrogenated block copolymer (A-Si) and the silane-modified hydrogenated block copolymer (B-Si) was obtained in the same manner as in Example 1, except that the hydrogenated block copolymer composition (polymer 2) obtained in Production Example 2 was used instead of the hydrogenated block copolymer composition (polymer 1) obtained in Production Example 1. An epoxy resin composition was then obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0209] Example 5 Epoxy resin compositions were obtained in the same manner as in Example 4, except that the amounts of the hydrogenated block copolymer composition, epoxy resin (C), and curing agent (D) used were changed as shown in Table 3, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0210] Example 6 An epoxy resin composition was obtained in the same manner as in Example 1, except that the hydrogenated block copolymer composition (Polymer 2) obtained in Production Example 2 was used instead of the silane-modified hydrogenated block copolymer composition (Silane-modified Polymer 1), and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0211] Comparative Example 1 A silane-modified hydrogenated block copolymer (B-Si) (silane-modified polymer 3) was obtained in the same manner as in Example 1, except that the hydrogenated block copolymer (B) (polymer 3) obtained in Production Example 3 was used instead of the hydrogenated block copolymer composition (polymer 1) obtained in Production Example 1. An epoxy resin composition was then obtained in the same manner as in Example 1, except that the silane-modified hydrogenated block copolymer (B-Si) (silane-modified polymer 3) was used instead of the silane-modified hydrogenated block copolymer composition (silane-modified polymer 1), and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0212] Comparative Example 2 Without using the hydrogenated block copolymer composition, the epoxy resin (C) and the curing agent (D) were quickly mixed at room temperature to obtain a mixture. Then, using the mixture obtained above instead of the epoxy resin composition, evaluation was carried out in the same manner as in Example 1. The results are shown in Table 3.

[0213] Comparative Example 3 A silane-modified hydrogenated block copolymer composition (silane-modified polymer 1) was obtained in the same manner as in Example 1. Then, the silane-modified hydrogenated block copolymer composition (silane-modified polymer 1) alone was used instead of the epoxy resin composition, and evaluation was carried out in the same manner as in Example 1. The results are shown in Table 3.

[0214] Comparative Example 4 A silane-modified hydrogenated block copolymer composition (silane-modified polymer 2) was obtained in the same manner as in Example 4. Then, the silane-modified hydrogenated block copolymer composition (silane-modified polymer 2) alone was used instead of the epoxy resin composition, and evaluation was carried out in the same manner as in Example 1. The results are shown in Table 3.

[0215] [Table 3]

[0216] As is clear from Table 3, the hydrogenated block copolymer compositions having the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B), the epoxy resin (C), and the curing agent (D) had excellent adhesion and impact absorption properties to a wide range of materials (Examples 1 to 6).

[0217] On the other hand, when the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) were not used in combination, and when the hydrogenated block copolymer composition was not used, the impact absorption properties were poor (Comparative Examples 1 and 2). Furthermore, when the hydrogenated block copolymer composition was used alone, the adhesiveness was poor (Comparative Examples 3 and 4).

Claims

1. An epoxy resin composition comprising: a hydrogenated block copolymer composition including a hydrogenated block copolymer (A) represented by the following general formula (A) and a hydrogenated block copolymer (B) represented by the following general formula (B); an epoxy resin (C); and a curing agent (D). Ar1 Ａ -HD Ａ -Ar2 Ａ (A) Ar1 Ｂ -HD Ｂ -Ar2 Ｂ (B) (In the general formula (A) and the general formula (B), Ar1 Ａ , Ar2 Ａ , Ar1 Ｂ , and Ar2 Ｂ is an aromatic vinyl polymer block, and HD Ａ and HD Ｂ is a hydrogenated polymer block of a conjugated diene polymer, and Ar1 Ａ Weight average molecular weight (Mw(Ar1 Ａ )) with respect to Ar2 Ａ Weight average molecular weight (Mw(Ar2 Ａ )) ratio (Mw(Ar2 Ａ ) / Mw(Ar1 Ａ )) is 3.0 to 20, and Ar1 Ｂ Weight average molecular weight (Mw(Ar1 Ｂ )) with respect to Ar2 Ｂ Weight average molecular weight (Mw(Ar2 Ｂ )) ratio (Mw(Ar2 Ｂ ) / Mw(Ar1 Ｂ )) is 0.95 to 1.

05.

2. 2. The epoxy resin composition according to claim 1, wherein the weight ratio (A / B) of the hydrogenated block copolymer (A) to the hydrogenated block copolymer (B) in the hydrogenated block copolymer composition is 10 / 90 to 80 / 20.

3. 3. The epoxy resin composition according to claim 1, wherein at least a part of the hydrogenated block copolymer constituting the hydrogenated block copolymer composition has a silane-containing functional group.

4. 3. The epoxy resin composition according to claim 1, wherein a weight ratio ((C+D) / (A+B)) of the total content of the epoxy resin (C) and the curing agent (D) to the total content of the hydrogenated block copolymer (A) and the hydrogenated block copolymer (B) is 99 / 1 to 70 / 30.

5. 3. The epoxy resin composition according to claim 1, wherein the proportion of aromatic vinyl monomer units in the hydrogenated block copolymer composition is 20 to 60% by weight based on the total weight of all polymer components.

6. 3. The epoxy resin composition according to claim 1, wherein the hydrogenation rate of the olefin in the hydrogenated block copolymer composition is 10 to 100%.

7. Ar1 in general formula (A) and general formula (B) Ａ , Ar1 Ｂ , and Ar2 Ｂ Each of the weight average molecular weights is 1,000 to 40,000, Ar2 in general formula (A) Ａ The weight average molecular weight of the copolymer is 5,000 to 250,000, HD in general formula (A) ａ and HD in general formula (B) ｂ 3. The epoxy resin composition according to claim 1, wherein each of the weight average molecular weights of

8. 3. The epoxy resin composition according to claim 1, wherein the weight average molecular weight of the hydrogenated block copolymer composition is 20,000 to 500,000.

9. 3. The epoxy resin composition according to claim 1, which is an adhesive for electronic substrates, a structural adhesive for automobiles, a structural adhesive for aircraft, a structural adhesive for sports components, or an interlayer for bulletproof vests.

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